POLYMERS

POLYMERS
The small molecules that combines with each other to form a macromolecule is called monomer, The
macromolecule formed is called polymer.

CLASSIFICATION OF POLYMERS :

(a) Based on source of availability :

(1) Natural : Protein, Nucleic acid, Cellulose

(2) Semi-synthetic : Cellulose diacetate

Polymers
(3) Synthetic : Fibre, plastic, synthetic rubber

(b) Based on mode of polymerisation :

(1) Homo-polymer (2) Addition or Condensation.
Homopolymer and copolymer : Homopolymers one polymers having single type of monomers.

n CH 2  CH 2 
 ( CH 2  CH 2 ) n
Polythene

 While the polymers of two or more than two types of monomers is called co-polymers.
e.g.
C6H5

n CH2 = CH CH = CH2 + n C6H5 CH = CH 2 (Styrene) CH2 – CH = CH – CH2 CH = CH

n
(3) Addition Polymers : This polymers is formed by monomer molecules having double or triple bond.
e.g. Polythene.
(4) Condensation Polymers : This polymer is formed by condensation of monomer with simultaneous
loss of small molecules like. H2O, NH3, alcohol etc.
e.g. Nylon 66.

H H
n N (CH2)6 N + n HO C CH2 4 COOH – N – (CH2)6 – N – C – (CH2)4 – C –
H H O H H O O
H O Adipic acid
2 Nylon 66 n

(c) Classification of polymers on the basis of Molecular force:

(i) Elastomers (ii) Fibre (iii) Thermoplast (iv) Thermosetting
(1) Elastomers : Polymers are held by weakest force.
 These weakest force causes stretching of the strected polymer to its normal size.
e.g.  valcanized rubber..
(2) Fibre : Has high tensile strength
 Has stronger intermolecular forces like H-bond
  Imparts crystalline nature, due to which it has sharp M.Pt. e.g.  Fibre
(3) Thermoplastics : Has intermediate force between elastomer and fibre
 Has no cross-links. e.g.  Polyethylene, Polystyrene.
(4) Thermosetting : This is relatively low molecular mass polymers of semi-fluids which on heating in a
mould becomes infusible hard mass.
 This happen due to extensive cross linking.
 Has three dimensional network of bonds. e.g.  Bakelite.

GENERAL METHODS OF POLYMERISATION :

1. Addition 2. Condensation
1. Addition :
The monomers are unsaturated alkene, alkadiene or their derivatives.
 The addition polymers can be classified into three types on the basis of its monomers.
1. Radical 2. Carbocation 3. Carbanion
 The addition polymerisation is also called as chain growth polymerisation, because it takes place
through stages leading to increase in chain-length and the each stage produces relatively reactive
intermediate which is used in next step.
(1) Free-Radical Addition Polymers : The free-radical polymers take place through initiator. Initiator
generates radical. e.g.

CH3 CH 3 CH 3
| | |
Homo
CH3  C  O  O  C  CH 3   2CH 3  C  O
| | |
CH3 CH 3 CH 3

Initiator (In)

Vinyl Polymensation : Obtained from CH 2  CH

|
G
Its formation can be depicted by given mechanism
1st Step: Chain initiator step :
 In 
Initiator 

In+ CH2 CH In CH2 CH

G G
2nd Step: Chain Propagation :

In CH2 CH + CH2 CH In CH 2 CH – CH 2 CH
G G G G
3rd Step : Termination :
. .
In–CH2–CH– CH2– CH + In In–CH2–CH––CH2– CH – In
n n n
G G G G
Concept of chain transfer agents :
Some times some other compounds present may compete with the parent addition chain reactions and it
initiates its non chain growth to simultaneously stop the normal polymerisation. Such reagents are called
chain transfer agents and it includes CCl4.
C6 H 2  CH  CH 2 , with normal initiator will form polystyrene but due to the presence of CCl4 the different
(Styrene)

polymeric product is formed.

Cl
|


1st Step : Cl  C  Cl  CCl3  Cl

|
Cl
Cl C6H5
 i  Cl& | |
2nd Step : C6 H 5 CH = CH 2 C6 H 5 CH CH  & 
 ii CCl Cl – C –– CH–CH 2–n

Chain Inhibitors :
If the chain transfer agent forms a radical which is highly unreactive, the reaction chain gets terminated.
Such compounds inhibit the polymerisation and they are -
(a) Phenol (b) Some amines (c) Quinoline
If the chain transfer agent is, Banzoquinone,
O OR OR

.
R +
. etc

O O
. O

Conjugated dienes : (1) 1, 2 diene (2) 1, 4 diene

(1) 1, 2 Polymerisation :

R––CH2 – CH – CH2 – CH
CH CH | |
2
R CH2 CH CH = CH2 CH CH
1 2 3 4
CH2 CH CH2 = CH R CH CH2 – R || ||
1 2 3 4 CH 2 CH 2 n

2. 1, 4 Polymers

. .
R + CH 2 CH CH = CH2 R – CH 2–– CH CH = CH2 R – CH2 CH = CH – CH2
1 2 3 4

R CH H
C C
H CH2
trans n
Cationic Addition Polymers :
(a) Chain reaction :
+
+
CH2 CH + H CH3 CH

G G
(b) Chain Propagation :
+ +
CH CH + CH CH CH3 CH CH2 CH
3

G G G G
(c) Chain termination : By Anions
–
CH3 CH CH CH + A CH3 – CH– CH–– CH – A

G n G n
G G

SOME COMMERCIALLY IMPORTANT

S.No. Name of Polymer Structure Monomer U ses

1. Polythene (CH 2  CH 2 ) n CH2 = CH2 As insulator, anticorrsoive,

packing material, household and
laboratory wares.
 Cl 
2. 
Polyvinylchloride (PVC)  |  CH2 = CHCl In manufacture of raincoats, hand
CH  CH 
 2 n
bags, vinyl flooring and leather
clothes.
3. Polytetrafluoro ethylene  CF2  CF2 n CF2 = CF2 As lubricant, insulator and making
(PTFE) or Teflon cooking wares.
 CH 2  C  CH  CH 2  CH2  C  CH  CH2
4. Neoprene  |  | As insulator, making conveyor
 Cl  Cl
 n
belts and printing rollers.